Heteroleptic NIR-Emitting Yb^III/Anilate-Based Neutral Coordination Polymer Nanosheets for Solvent Sensing

Abstract

Nanosheets of two mixed linker (anilate/carboxylate)/Yb III -based two-dimensional (2D) layered coordination polymers (CPs) are herein reported. Bulky sized CPs, formulated as [Yb 4 (ClCNAn) 5 (DOBDC) 1 (DMSO) 10 ] n •(DMSO) 2 (1) and [Yb 2 (ClCNAn) 2 (F 4 BDC)(DMSO) 6 ] n (2), are formed by twodimensional neutral polymeric networks based on Yb III ions, heterosubstituted ClCNAn 2− anilate, and dicarboxylate linkers (DOBDC 2− in 1; F 4 BDC 2− in 2): in 1, neighbor layers are eclipsed and form six-membered rings showing either hexagonal cavities, formed by ClCNAn 2− and Yb III ions or rectangular cavities formed by ClCNAn 2− , DOBDC 2− , and Yb III while distorted square-like cavities formed by ClCNAn 2− , F 4 BDC 2− , and Yb III are obtained in 2. The 1 and 2 nanosheets, that is, 1-NS and 2-NS, are produced by exfoliation of bulk CPs by the wellknown top-down approach and characterized by atomic force microscopy and high resolution transmission electron microscopy.The 1-NS and 2-NS show thickness in the range of 1−5 nm, whereas the lateral dimensions are in the micrometer scale and the presence of well-defined lattice fringes, key evidence of their robustness. Remarkably the powder X-ray diffraction (PXRD) patterns highlight that the crystallinity is retained at the nanoscale level. Nanosheets photophysics are investigated by an innovative Multiprobe Approach where lifetime, photoluminescence (PL) and integrated PL are simultaneously measured in order to study how these parameters can be affected by the presence of the different ligands. These advanced photophysical studies pave the way to challenging luminescent sensing applications and to contribute to the ongoing research on fabricating robust and crystalline hybrid (organic/inorganic) lanthanide sheetlike 2D nanomaterials.

Slow Relaxation of the Magnetization in Anilato-Based Dy(III) 2D Lattices

“…In recent years, anilato-derivative ligands (3,6-disubstituted of the 2,5-dihydroxy-1,4-benzoquinone dianion = C 6 O 4 X 2 2− , Scheme 1 a) have been combined with Ln(III) ions to prepare coordination polymers with interesting optical [ 40 , 41 , 42 , 43 ] or magnetic properties, including SMMs [ 33 , 44 , 45 , 46 ].…”

Heteroleptic LaIII Anilate/Dicarboxylate Based Neutral 3D-Coordination Polymers

“…Additionally, the anilate ligands have a stronger affinity toward the La(III) ion than the carboxylate one. This assertion was forecasted by the authors of [7].…”

“…Additionally, the anilate ligands have a stronger affinity toward the La(III) ion than the carboxylate one. This assertion was forecasted by the authors of [7]. The interaction Yb(III)/anilate/dicarboxylate with stoichiometric (2:1:1) ratio in the reaction produces coordination polymers with the 2:2.5:0.5 or 2:2:1 formula ratios [7].…”

“…The interaction Yb(III)/anilate/dicarboxylate with stoichiometric (2:1:1) ratio in the reaction produces coordination polymers with the 2:2.5:0.5 or 2:2:1 formula ratios [7]. A significant increase in the content of dicarboxylic acid in the reaction mixture makes it possible to obtain a polymer with a component ratio of La(III)/anilate/dicarboxylate-2:2:4, which dramatically affects the resulting CPs' structures.…”

Designing Magnetic NanoMOFs for Biomedicine: Current Trends and Applications

“…Metal-organic frameworks (MOFs) are crystalline porous compounds formed by the self-assembling of metal ions and organic linkers [1][2][3]. Due to the possibility to tailor their composition by a proper choice of metal ions [4] and organic linkers, it can be possible to develop MOFs with applications in many areas, such as catalysis, sensing, gas-separation/adsorption/detection, information storage and telecommunications [5][6][7][8][9][10][11][12][13][14][15]. Furthermore, the possibility to miniaturize MOFs up to the nanoscale level, nanoMOFs, makes them interesting candidates in biomedicine due to their unique chemical and physical properties, i.e., high surface area, easy to functionalize and large pore sizes [16].…”